Access paths are somewhat obsolete feature of OPC Data Access specification, and few OPC servers actually use it; but if a particular OPC server does use access paths, specifying the proper access path together with ItemID may be the only way to retrieve the data you want.
If you want to retrieve a list of possible access paths available for a specific OPC item, call the BrowseAccessPaths method, passing it the information about the OPC server, and the ItemID. You will receive back an array of strings; each element of this array is an access path that you can use with methods such as ReadItem or SubscribeItem.
In OPC Data Client.NET, you can also pass the access path to a constructor of DAItemDescriptor object and later use that descriptor with various methods.